CN107552093A - A kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification - Google Patents
A kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification Download PDFInfo
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- CN107552093A CN107552093A CN201710764217.3A CN201710764217A CN107552093A CN 107552093 A CN107552093 A CN 107552093A CN 201710764217 A CN201710764217 A CN 201710764217A CN 107552093 A CN107552093 A CN 107552093A
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Abstract
This hair discloses a kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification, and prepared composite load benzoxazole iridium hydrotalcite catalyst is synthesized by following two classes iridium complex.Wherein hydrotalcite supports (layer dihydroxy complex hydroxide) have the characteristics that the adjustable denaturation of the Modulatory character of the Nomenclature Composition and Structure of Complexes, acid-base property and the adjustable denaturation that interacts, it is considered as the splendid carrier of nanometer iridium, this catalyst has very high heat endurance and catalytic activity, is advantageous to catalyze and synthesize Bisphenol F and esterification.And convenient recovery, reduce production cost, it is expected to as the cleaning procedure route of great competitiveness.
Description
Technical field
The present invention relates to a kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification, this catalyst
With very high heat endurance and catalytic activity, be advantageous to catalyze and synthesize Bisphenol F and convenient recovery, simultaneously for Bisphenol F
Synthetic reaction and esterification also show good property.
Background technology
Hydrotalcite is ion functional's clay that a kind of interlayer ion has interchangeability.Due to hydrotalcite layered structure
Particularity, show the special properties such as adjustable denaturation and interchangeability, the alkalescence of ion.These unique structures of hydrotalcite
Property, a kind of supported materials for having and there is very big application potential are become, it is of increased attention with applying.Mesh
Before, hydrotalcite material has in catalysis, biology, environmental protection, additive, medicine and functional high molecule material etc. widely should
With., can be by some metal iridiums using the interchangeability of hydrotalcite layers anion and the high activity of metal iridium complex catalyst
Complex catalyst is inserted into hydrotalcite layers, and the iridium supported catalyst being prepared not only has higher catalytic activity, and
Catalyst is easily isolated after completion of the reaction, avoids such iridium catalyst and product purity is impacted, it also avoid simultaneously
Heavy metal pollution is caused to environment.The eka-iridium supported catalyst also has very high heat endurance, still has after recycled for multiple times
There is very high activity.
Bisphenol F and triacetin ester compounds are all high added value products, their synthesis mainly using strong acid or
Solid acid catalyst, the problems such as environmental pollution cost is high be present.Also bring along serious equipment corrosion problem.Therefore, find
Catalyst can be replaced to have become current research and the focus of exploitation.
In order to solve the above problems, based on the present invention is using hydrotalcite and two metal iridium compounds, it is prepared for compound
Benzoxazole iridium hydrotalcite catalyst is loaded, for catalyzing and synthesizing Bisphenol F and acetin, the method has not yet to see report.
The content of the invention
The invention discloses a kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification.Ours
Found in research, this composite catalyst is advantageous to catalyzing and synthesizing for Bisphenol F and acetin.
The technical scheme provided according to invention, prepared composite load benzoxazole iridium hydrotalcite catalyst is by following
The synthesis of two class iridium complexs：
The invention provides a kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification, specific and conjunction
It is as follows into step:
(1) solvent-thermal method is first used, by benzoxazole part and iridous chloride with 1:1~30:1 ratio is dissolved in 1:1
~30:In the ethylene glycol ethyl ether of 1 ratio and the mixed solution of water, 25~500 DEG C are stirred and heated under special gas protection, stirring
After 1~48h, suction filtration obtains iridium complex BO.By BO and PEt3With 1:1~1:20 ratio is blended in absolute ethyl alcohol and the tert-butyl alcohol
In the mixed solvent, stir 4~12h at room temperature, heat 2~12h with reactor at 50~110 DEG C, centrifugal drying produced
Thing BOP.
(2) by BO and hydrotalcite (HT) 1:1~1:20 ratio is blended in deionized water, absolute ethyl alcohol and the tert-butyl alcohol it is mixed
In bonding solvent, 1~48h is stirred at room temperature, 1~72h is heated with reactor at 20~500 DEG C, and centrifugal drying obtains product BO@
HT。
(3) by BOP and BO@HT with 1:1~1:30 ratio is blended in deionized water, the mixing of absolute ethyl alcohol and the tert-butyl alcohol
In solvent, 1~48h is stirred at room temperature, 1~72h is heated with reactor at 20~600 DEG C, and centrifugal drying obtains product BO@
BOP@HT。
Further, the special gas in above-mentioned steps (1) are carried out under the protection of such as nitrogen, argon gas etc..
Further, in above-mentioned steps, programming rate is 0.1~10 DEG C/min.
Above-mentioned composite load iridium catalyst BO@BOP@HT Bisphenol F applications, it is characterised in that：By 4g phenol, 1g NEW TYPE OF COMPOSITEs
Iridium catalyst is added in 10mL dimethylbenzene, is stirred at room temperature, then be slowly added dropwise 1：1 10% HCl and 37% formalin 4mL
Mixed solution, 100 DEG C are heated to, react 2h.Then by resulting reacting liquid filtering, catalyst is reclaimed.The liquid being filtrated to get
Body is crude product.Gained crude product by rotating recycling design, being evaporated under reduced pressure and reclaim remaining phenol, remaining product is used back
The solvent recrystallization of receipts once, obtains Bisphenol F.
The application of above-mentioned composite load iridium catalyst BO@BOP@HT catalyzing glycerols and acid esterification reaction, it is characterised in that：
By glycerine and acetic acid according to molar ratio of alcohol to acid 1:2~1:7 add in reactor, and it is anti-to add 30~50mL toluene and quality
The composite load iridium catalyst BO@BOP@HT of the 0.6~5% of thing gross mass are answered, are 100 DEG C~140 DEG C in reaction temperature, backflow
Divide water, 2~8h of stirring reaction, obtain the mixture containing acetin.
Brief description of the drawings
Composite load iridium catalyst BO BOP HT prepared by Fig. 1 present invention ESEM collection of illustrative plates.
Embodiment
The composite of this modification provided by the invention can significantly improving Bisphenol F and triacetin Lipase absobed production
Rate, and the preparation technology of catalyst is simple, it is green.
Hereinafter, applicant has done specific experiment to the present invention.These are only used for elaborating the present invention, not with any side
The scope of formula limitation invention.
Embodiment one：A kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification, including following technique
Step：
(1) solvent-thermal method is first used, by benzoxazole part and iridous chloride with 1:1 ratio is dissolved in 1:1 ratio
In the mixed solution of ethylene glycol ethyl ether and water, 25~500 DEG C are stirred and heated under special gas protection, after stirring 48h, is filtered
To iridium complex BO.By BO and PEt3With 1:1 ratio is blended in the in the mixed solvent of absolute ethyl alcohol and the tert-butyl alcohol, stirs at room temperature
4h is mixed, 12h is heated with reactor at 110 DEG C, centrifugal drying obtains product BOP.
(2) by BO and hydrotalcite (HT) 1:20 ratio is blended in deionized water, and the mixing of absolute ethyl alcohol and the tert-butyl alcohol is molten
In agent, 24h is stirred at room temperature, 48h is heated with reactor at 400 DEG C, and centrifugal drying obtains product BO@HT.
(3) by BOP and BO@HT with 1:30 ratio is blended in the mixed solvent of deionized water, absolute ethyl alcohol and the tert-butyl alcohol
In, 48h is stirred at room temperature, 12h is heated with reactor at 400 DEG C, and centrifugal drying obtains product BO@BOP@HT.
Embodiment two：A kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification, including following technique
Step：
(1) solvent-thermal method is first used, by benzoxazole part and iridous chloride with 1:2 ratio is dissolved in 1:2 ratios
In the mixed solution of ethylene glycol ethyl ether and water, 25~500 DEG C are stirred and heated under special gas protection, after stirring 36h, is filtered
To iridium complex BO.By BO and PEt3With 1:1 ratio is blended in the in the mixed solvent of absolute ethyl alcohol and the tert-butyl alcohol, stirs at room temperature
4h is mixed, 12h is heated with reactor at 110 DEG C, centrifugal drying obtains product BOP.
(2) by BO and hydrotalcite (HT) 1:20 ratio is blended in deionized water, and the mixing of absolute ethyl alcohol and the tert-butyl alcohol is molten
In agent, 24h is stirred at room temperature, 36h is heated with reactor at 300 DEG C, and centrifugal drying obtains product BO@HT.
(3) by BOP and BO@HT with 1:20 ratio is blended in the mixed solvent of deionized water, absolute ethyl alcohol and the tert-butyl alcohol
In, 36h is stirred at room temperature, 12h is heated with reactor at 300 DEG C, and centrifugal drying obtains product BO@BOP@HT.
Embodiment three：4g phenol, 1g NEW TYPE OF COMPOSITEs iridium catalyst are added in 10mL dimethylbenzene, stirred at room temperature, then delay
It is slow to be added dropwise 1：1 10% HCl and 37% formalin 4mL mixed solutions, 100 DEG C are heated to, react 2h.Then by obtained by
Reacting liquid filtering, reclaim catalyst.The liquid being filtrated to get is crude product.Gained crude product by rotate recycling design,
It is evaporated under reduced pressure and reclaims remaining phenol, remaining product is recrystallized once with recovered solvent, obtains Bisphenol F.Yield is 86%
Example IV：In 250mL round-bottomed flasks, 0.1mol glycerine, 0.6mol acetic acid and 40mL toluene are added, is added
0.3g catalyst BO@BOP@HT, it is 110 DEG C in reaction temperature, reflux water-dividing, stirring reaction 2h, through chromatography, glycerine turns
Rate is 99%, and the selectivity of diacetine is 83%, and the selectivity of glyceryl triacetate is 14%.
Embodiment five：Composite load iridium catalyst BO@BOP@HT recycling：
In 250mL round-bottomed flasks, 0.1mol glycerine, 0.6mol acetic acid and 40mL toluene are added, adds returning for 0.3g
The catalyst BO@BOP@HT of receipts, it is 110 DEG C in reaction temperature, reflux water-dividing, stirring reaction 2h, through chromatography, glycerine conversion
Rate is 99%, and the selectivity of diacetine is 83%, and the selectivity of glyceryl triacetate is 13%.
Claims (3)
1. the invention discloses a kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification；
The technical scheme provided according to invention, prepared composite load benzoxazole iridium hydrotalcite catalyst is by following two class
Iridium complex synthesis：
The invention provides a kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification, specific and synthesis step
It is rapid as follows:
(1) solvent-thermal method is first used, by benzoxazole part and iridous chloride with 1:1~30:1 ratio is dissolved in 1:1~30:
In the ethylene glycol ethyl ether of 1 ratio and the mixed solution of water, 25~500 DEG C are stirred and heated under special gas protection, stirring 1~
After 48h, suction filtration obtains iridium complex BO；By BO and PEt3With 1:1~1:20 ratio is blended in absolute ethyl alcohol and the tert-butyl alcohol
In the mixed solvent, 4~12h being stirred at room temperature, 2~12h being heated with reactor at 50~110 DEG C, centrifugal drying obtains product
BOP。
(2) by BO and hydrotalcite (HT) 1:1~1:20 ratio is blended in deionized water, and the mixing of absolute ethyl alcohol and the tert-butyl alcohol is molten
In agent, 1~48h is stirred at room temperature, 1~72h is heated with reactor at 20~500 DEG C, and centrifugal drying obtains product BO@HT.
(3) by BOP and BO@HT with 1:1~1:30 ratio is blended in the mixed solvent of deionized water, absolute ethyl alcohol and the tert-butyl alcohol
In, 1~48h is stirred at room temperature, 1~72h is heated with reactor at 20~600 DEG C, and centrifugal drying obtains product BO@BOP@
HT；
Further, the special gas in above-mentioned steps (1) are carried out under the protection of such as nitrogen, argon gas etc.；
Further, in above-mentioned steps, programming rate is 0.1~10 DEG C/min.
2. above-mentioned composite load iridium catalyst BO@BOP@HT Bisphenol F applications, it is characterised in that：By 4g phenol, 1g NEW TYPE OF COMPOSITE iridium
Catalyst is added in 10mL dimethylbenzene, is stirred at room temperature, then be slowly added dropwise 1：1 10% HCl and 37% formalin 4mL is mixed
Solution is closed, is heated to 100 DEG C, reacts 2h.Then by resulting reacting liquid filtering, catalyst is reclaimed；The liquid being filtrated to get
For crude product；Gained crude product by rotating recycling design, being evaporated under reduced pressure and reclaim remaining phenol, remaining product recovery
Solvent recrystallization once, obtain Bisphenol F.
3. above-mentioned composite load iridium catalyst BO@BOP@HT catalyzing glycerols and the application of acid esterification reaction, it is characterised in that：Will
Glycerine and acetic acid are according to molar ratio of alcohol to acid 1:2~1:7 add in reactor, and toluene and the quality for adding 30~50mL are reaction
The composite load iridium catalyst BO@BOP@HT of the 0.6~5% of thing gross mass, it is 100 DEG C~140 DEG C in reaction temperature, backflow point
Water, 2~8h of stirring reaction, obtain the mixture containing acetin.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111974457A (en) * | 2020-08-31 | 2020-11-24 | 江南大学 | Catalyst for synthesizing substituted ketone compound and preparation method thereof |
| CN112169842A (en) * | 2020-10-27 | 2021-01-05 | 江南大学 | Novel efficient supported Au/GO catalyst and preparation method and application thereof |
| CN115193479A (en) * | 2021-04-27 | 2022-10-18 | 江南大学 | PBS microsphere loaded metal iridium catalyst, preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111974457A (en) * | 2020-08-31 | 2020-11-24 | 江南大学 | Catalyst for synthesizing substituted ketone compound and preparation method thereof |
| CN111974457B (en) * | 2020-08-31 | 2021-05-28 | 江南大学 | Catalyst for synthesizing substituted ketone compound and preparation method thereof |
| CN112169842A (en) * | 2020-10-27 | 2021-01-05 | 江南大学 | Novel efficient supported Au/GO catalyst and preparation method and application thereof |
| CN115193479A (en) * | 2021-04-27 | 2022-10-18 | 江南大学 | PBS microsphere loaded metal iridium catalyst, preparation method and application |
| CN115193479B (en) * | 2021-04-27 | 2023-10-27 | 江南大学 | PBS microsphere supported metal iridium catalyst and preparation method and application thereof |
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Effective date of registration: 20210721 Address after: 257000 Haike academy, west of HaoChun Road, Shikou Town, Dongying District, Dongying City, Shandong Province Patentee after: Shandong Yike Chemical Co.,Ltd. Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Patentee before: Jiangnan University |
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